Protected aminofunctionalized polymerization initiators and methods of making and using same

ABSTRACT

Anionic polymerization initiators useful in the preparation of polymers having a protected amine functional group. The amine functionality includes a first protecting group, which can be aralkyl, methyl, allyl or tertiary alkyl group. The other of the amine protecting groups can be the same as the first protecting group. Alternatively, the second protecting group can be different from the first protecting group, in which case it is selected to have differential stability to agents used to remove the aralkyl, methyl, allyl or tertiary alkyl protecting group.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation of U.S. application Ser. No.09/655,528, filed Sep. 19, 2000, which is a continuation-in-part of U.S.application Ser. No. 09/256,737, filed Feb. 24, 1999, the disclosures ofwhich are incorporated by reference herein in their entireties.

FIELD OF THE INVENTION

[0002] The present invention relates to polymerization initiators, andmore particularly to anionic polymerization initiators having protectedamine functionality, as well as processes for making and using the sameand polymers prepared using the initiators.

BACKGROUND OF THE INVENTION

[0003] Olefinic containing monomers can be polymerized usingorgano-alkali metal initiators, such as butyllithium. The resultantintermediate polymer contains an active alkali metal end group, whichcan be subsequently reacted with a suitable protonating,functionalizing, or coupling or linking agent to replace the alkalimetal with a more stable end group. In many applications, it can beuseful to react the polymer living end with a functionalizing agent,such as ethylene oxide, to provide a polymer having a terminalfunctional group, such as a hydroxyl, carboxyl, or amine group.

[0004] Telechelic polymers contain two functional groups per molecule atthe termini of the polymer and are useful in a variety of applications.For example, telechelic polymers have been employed as rocket fuelbinders, in coatings and sealants, and in adhesives. One approach thathas been used to prepare telechelic polymers is the generation andsubsequent functionalization of a “dilithium initiator.” A dilithiuminitiator can be prepared by the addition of two equivalents ofsecondary butyllithium to meta-diisopropenylbenzene. The dilithiuminitiator is then reacted with suitable monomers, such as butadiene, toform a polymer chain with two anionic sites. The resultant polymer chainis then reacted with two equivalents of a functionalizing agent such asethylene oxide.

[0005] While useful, gelation is frequently observed during thefunctionalization step. This leads to lower capping efficiencies (see,for example, U.S. Pat. No. 5,393,843, Example 1, wherein the cappingefficiency was only 82%). Additional details of this gelation phenomenaare described in U.S. Pat. No. 5,478,899. Further, this dilithiumapproach can only afford telechelic polymers with the same functionalgroup on each end of the polymer chain.

[0006] Progress has been made in the synthesis of dihydroxy terminatedpolymers. For example, monofunctional silyl ether initiators containingalkali metal end groups are disclosed in GB 2,241,239. Thesemonofunctional silyl ether initiators were demonstrated to be useful inproducing polybutadienes having an alpha protected hydroxyl functionalgroup. The living polymer can be reacted with suitable functionalizingagent such as ethylene oxide, and the silyl protecting group removed toprovide a dihydroxy telechelic polymer.

[0007] Monofunctional ether initiators of the formula M-Z-O—C(R¹R²R³)wherein M is an alkali metal, Z is a branched or straight chainhydrocarbon tether group, and R¹, R² and R³ are independently defined ashydrogen, alkyl, substituted alkyl, aryl or substituted aryl, have alsobeen proposed as anionic polymerization initiators to introduce aprotected hydroxyl functionality into a polymer. See U.S. Pat. No.5,621,149. The hydrocarbon solubility of such initiators can beincreased by chain extension of the initiator with a conjugated diene.See U.S. Pat. No. 5,565,526.

[0008] Anionic initiators containing a tertiary amine functionality havealso been proposed for use in hydrocarbon solvent polymerizations. Suchinitiators have the general formula

M-Z-N—(C—R¹R²R³)₂

[0009] wherein M is defined as an alkali metal selected from lithium,sodium and potassium; Z is defined as a branched or straight chainhydrocarbon connecting group which contains 3-25 carbon atoms; and R¹,R² and R³ are independently defined as hydrogen, alkyl, substitutedalkyl groups, aryl or substituted aryl groups. See M. J. Stewart, N.Shepherd, and D. M. Service, Brit. Polym. J., 22, 319-325 (1990).

[0010] However, these amine functional initiators possess low solubilityin hydrocarbon solvents (typically less than 0.3 Molar in aliphatic orcycloaliphatic solvents like hexane or cyclohexane). The addition of anethereal co-solvent does increase the solubility of these initiators;however, this also increases the amount of 1,2-microstructure in theresultant polymer. See H. L. Hsieh and R. P. Quirk, AnionicPolymerization Principles and Practical Applications, pp. 397-400.Various other techniques have been employed to increase the solubilityof these initiators in hydrocarbon solvent. For example, chain extensionof the initiator with a conjugated diene increased the solubilityseveral fold. See U.S. Pat. No. 5,527,753.

[0011] The synthesis of diamino terminated polymers remains relativelyunexplored. Nakahama reports the preparation of amino terminatedpolystyrene by trapping the dianion with an electrophile that containeda protected amine group. A high degree of functionality was achieved bythis technique. See K. Ueda, A. Hirao, and S. Nakahama, Macromolecules,23, 939-945 (1990). However, the reaction conditions (−78° C., THFsolvent) were not practical for commercial production of thesefunctionalized polymers.

[0012] El-Aasser et al. recently reported the preparation of aminoterminated telechelic polybutadiene by a free radical approach. See J.Xu, V. L. Dimonie, E. D. Sudol, and M. S. El-Aasser, Journal of PolymerScience: Part A: Polymer Chemistry, 33, 1353-1359 (1995). Since this isa free radical synthesis, little control of molecular weight, molecularweight distribution, and position of the amine functional group wasobtained.

SUMMARY OF THE INVENTION

[0013] The present invention relates to protected amine functionalizedinitiators and processes for making and using the same to prepare aminefunctionalized polymers. The initiators of the invention include atertiary amine functionality. The amine functionality includes twoprotecting groups, which may be the same or different. When theprotecting groups are different, the groups are selected so as to havedifferential stability under specified deprotection conditions.Accordingly one of the protecting groups can be selectively removedwithout removing the other protecting group. In this manner, secondaryamine functionalized polymers can be readily prepared.

[0014] Specifically the initiators of the invention include compounds ofthe formula:

[0015] wherein:

[0016] M is an alkali metal selected from the group consisting oflithium, sodium and potassium;

[0017] Z is a branched or straight chain hydrocarbon connecting groupwhich contains 3-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

[0018] Q is a saturated or unsaturated hydrocarbyl group derived by theincorporation of one or more unsaturated organic compounds, such as oneor more compounds selected from the group consisting of conjugated dienehydrocarbons, alkenylsubstituted aromatic compounds, and mixturesthereof, into the M-Z linkage;

[0019] n is from 0 to 5;

[0020] R¹ is a protecting group selected from the group consisting ofaralkyl, allyl, tertiary alkyl, and methyl; and

[0021] R² can be the same as R¹, with the proviso that when R¹ ismethyl, R² is not C1-C4 alkyl, or R² can be different from R¹, in whichcase R² is selected from the group consisting of alkyl, substitutedalkyl, alkoxy, substituted alkoxy, aryl, substituted aryl, heteroaryl,substituted heteroaryl, cycloalkyl, substituted cycloalkyl,heterocycloalkyl, and substituted heterocycloalkyl, with the provisothat when R² is not the same as R¹, then R² is more stable underconditions used to remove R¹,

[0022] or R¹ and R² together with the nitrogen atom to which they areattached form

[0023]  wherein y is from 1 to 4 and each R¹¹ is independently selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl, aryl,substituted aryl, cycloalkyl, substituted cycloalkyl, alkoxy,substituted alkoxy, heteroaryl, substituted heteroaryl,heterocycloalkyl, and substituted heterocycloalkyl.

[0024] In especially advantageous embodiments of the invention, theprotecting group R¹ is aralkyl, preferably benzyl or a benzylderivative; allyl; or tertiary alkyl, preferably tertiary butyl. In thisaspect of the invention, advantageously R² is the same as R¹.Alternatively, in this aspect of the invention, R² is methyl. Examplesof initiators of the invention include without limitation3-[(N-benzyl-N-methyl)amino]-1-propyllithium,3-[(N,N-dibenzyl)amino]-1-propyllithium,3-[(N-tert-butyl-N-methyl)amino]-1-propyllithium,3-[(N,N-di-tert-butyl)amino]-1-propyllithium, and mixtures thereof.

[0025] These initiators can be treated with organometallic compounds,containing Mg, Zn, B, Al, and the like, to potentially afford highersolubility of the initiators in hydrocarbon solutions and/or livingpolymer stabilization. Other additives, such as those disclosed incopending U.S. Ser. No. 09/149,952, filed Sep. 9, 1998, and Ser. No.09/512,494, filed Feb. 24, 2000, the entire disclosure of each of whichis hereby incorporated by reference, can also be used to improveinitiator solubility and/or living polymer stabilization.

[0026] The initiators are useful in polymerizing monomers capable ofanionic polymerization, including but not limited to conjugated dienessuch as butadiene and isoprene, alkenylsubstituted aromatic compoundssuch as styrene, and mixtures thereof, to generate mono-, homo- orhetero-telechelic alpha amine functionalized polymers. The molecularweight of the polymers can vary widely, typically ranging from about 500up to 10,000,000, although the polymers can have a molecular weightoutside of this range as well. Advantageously the polymers have amolecular weight ranging from about 500 to about 20,000. The polymerscan also have a variety of microstructures. For some applications, thepolymers may have a 1,2 vinyl content ranging from about 20 to about80%. Again, however, the invention includes polymers having a 1,2 vinylcontent outside of this range, for example, from about 80% to about 100%1,2 vinyl content or less than about 20% 1,2 vinyl content to theminimum 1,2 vinyl content that can be achieved (currently about 4-5%).

[0027] The polymers of the invention initially have an alpha tertiaryamine functionality. The protecting group R¹ is selected so that theprotecting group can be readily removed (or the amine functionality“deprotected”) under select conditions suitable for removing theprotecting group. For example, benzyl and benzyl derived protectinggroups can be removed under conditions used to hydrogenate unsaturationin the polymer chain. An allyl protecting group can be removed utilizinga rhodium catalyst. Methyl protecting groups can be removedphotochemically. Tertiary alkyl protecting groups can be removed by acidcatalyzed deprotection techniques.

[0028] As noted above, R² can be the same as R¹. In this aspect of theinvention, the resultant alpha tertiary amine functionalized polymerscan be treated to substantially simultaneously remove both R¹ and R² togive a polymer having an alpha primary amine functionality.

[0029] Alternatively, R¹ and R² are not the same. In this aspect of theinvention, R² is selected from suitable substituents which are morestable under the conditions used to remove R¹. As a result, R¹ can beremoved while R² remains intact to give an alpha secondary aminefunctionalized polymer. The alpha secondary amine functionalized polymercan be further treated to remove R², thus giving an alpha primary aminefunctionalized polymer.

[0030] The living polymers can be further treated to quench orfunctionalize the living end thereof, for example, to provide nearquantitative omega functionalized polymers (having for example hydroxyl,sulfide, carboxyl or other functionality). The polymers also havesubstantially homogeneous backbones, in contrast to polymers produced,for example, using dilithium initiator technology in which polymersinclude a cross linked core.

[0031] The polymers can be hydrogenated to give a liquid, processablefunctionalized polymer. In one advantageous aspect of the invention, anunsaturated polymer of the invention having a protected alpha tertiaryamine functionality in which R¹ (and optionally R² as well) is benzyl ora benzyl derivative can be modified by replacing (or partiallyreplacing) the protecting group with a hydrogen atom using hydrogenationto concurrently saturate the polymer and remove the benzyl protectinggroup(s) to afford a saturated polymer with an alpha primary orsecondary amine functionality. The hydrogenation step can be performedfor polymers having reactive or non-reactive functionality at the omegaposition of the polymer chain.

[0032] Thus the present invention provides polymers containing an alphaprimary, secondary or tertiary amine functionality, optionally with areactive or non-reactive functionality at the omega position of thepolymer chain. Such polymers can be hydrogenated to afford a saturated(or partially saturated polymer) with an alpha primary, secondary ortertiary amine functionality. The protecting group can be present ordisplaced for the saturated or unsaturated polymers, depending upon thenature of the protecting group and the types of deprotection conditionsrequired to remove the same.

[0033] Examples of the types of polymers, without limitation that can beprepared in accordance with the present invention are illustrated below:

DETAILED DESCRIPTION OF THE INVENTION

[0034] The present invention now will be described more fullyhereinafter with reference to the preferred embodiments of theinvention. This invention may, however, be embodied in many differentforms and should not be construed as limited to the embodiments setforth herein; rather, these embodiments are provided so that thisdisclosure will be thorough and complete, and will fully convey thescope of the invention to those skilled in the art.

[0035] The present invention provides novel anionic initiators, whichcan be hydrocarbon soluble, and mixtures of such initiators, containinga tertiary amino group and having the following general structure:

[0036] wherein:

[0037] M is an alkali metal selected from the group consisting oflithium, sodium and potassium;

[0038] Z is a branched or straight chain hydrocarbon connecting groupwhich contains 3-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

[0039] Q is a saturated or unsaturated hydrocarbyl group, and can bederived by the incorporation of one or more unsaturated organiccompounds, such as one or more compounds selected from the groupconsisting of conjugated diene hydrocarbons, alkenylsubstituted aromaticcompounds, and mixtures thereof, into the M-Z linkage;

[0040] n is from 0 to 5;

[0041] R¹ is a protecting group selected from the group consisting ofaralkyl, preferably benzyl or benzyl derivative, allyl, tertiary alkyl,preferably tertiary butyl, and methyl; and

[0042] R² can be the same as R¹, with the proviso that when R¹ ismethyl, R² is not C1-C4 alkyl, or R² can be different from R¹, in whichcase R² is selected from the group consisting of alkyl, substitutedalkyl, alkoxy, substituted alkoxy, aryl, substituted aryl, heteroaryl,substituted heteroaryl, cycloalkyl, substituted cycloalkyl,heterocycloalkyl, and substituted heterocycloalkyl, with the provisothat when R² is not the same as R¹, then R² is more stable underconditions used to remove R¹,

[0043] or R¹ and R² together with the nitrogen atom to which they areattached form

[0044]  wherein y is from 1 to 4 and each R¹¹ is independently selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl, aryl,substituted aryl, cycloalkyl, substituted cycloalkyl, alkoxy,substituted alkoxy, heteroaryl, substituted heteroaryl,heterocycloalkyl, and substituted heterocycloalkyl.

[0045] The term “aralkyl” generally refers to aralkyl groups in whichthe total number of carbon atoms is no greater than about 18. The termaralkyl includes groups in which the alkylene chain and/or the aryl ringcan include one or more heteroatoms, such as oxygen, nitrogen andsulfur. The alkylene chain and/or aryl ring can also be substituted withone or more groups such as C1-C4 alkyl, C1-C4 alkoxy, and the like, solong as the group does not interfere with the functionality of thebenzyl protecting group and its removal, and/or with the activity of thelithium living end of the initiator.

[0046] Advantageous aralkyl groups in accordance with the invention arebenzyl groups and benzyl derivatives. Benzyl derivatives include groupsin which the phenyl ring is substituted with one or more groups such asC1-C4 alkyl, C1-C4 alkoxy, and the like, so long as the group does notinterfere with the functionality of the benzyl protecting group and itsremoval, and/or with the activity of the lithium living end of theinitiator. The term benzyl derivative also refers to benzyl groups inwhich the methylene linkage may also be substituted, for example, withone or more groups such as C1-C4 alkyl, C1-C4 alkoxy, aryl (phenyl) andthe like, again so long as the group does not interfere with thefunctionality of the benzyl protecting group and its removal, and/orwith the activity of the lithium living end of the initiator. Benzylderivatives also include groups in which the ring and/or methylene chaincan include heteroatoms, such as oxygen, sulfur or nitrogen. Suchsubstituted benzyl protecting groups can be represented by the generalformula:

[0047] in which n is from 1 to 5; and each R and R′ is independentlyselected from the group consisting of hydrogen, alkyl, substitutedalkyl, aryl, substituted aryl, cycloalkyl, substituted cycloalkyl,alkoxy, substituted alkoxy, heteroaryl, substituted heteroaryl,heterocycloalkyl, substituted heterocycloalkyl, and the like, or atleast one R in combination with the phenyl ring forms a cyclic orbicyclic structure, such as

[0048] Exemplary R and R′ groups include without limitation methoxy,phenyl, methoxyphenyl, and the like. Exemplary substituted benzylsubstituents include without limitation 4-methoxybenzyl,2,4-dimethoxybenzyl, diphenylmethyl, 4-methoxyphenylmethyl,triphenylmethyl, (4-methoxylphenyl)diphenylmethyl, and the like.

[0049] As used herein, the term “alkyl” refers to straight chain andbranched C1-C25 alkyl. The term “substituted alkyl” refers to C1-C25alkyl substituted with one or more lower C1-C10 alkyl, lower alkoxy,lower alkylthio, or lower dialkylamino. The term “cycloalkyl” refers toone or more rings, typically of 5, 6 or 7 atoms, which rings may befused or unfused, and generally including 3 to 12 carbon atoms. The term“substituted cycloalkyl” refers to cycloalkyl as defined above andsubstituted with one or more lower C1-C10 alkyl, lower alkoxy, loweralkylthio, or lower dialkylamino. The term “aryl” refers to C5-C25 arylhaving one or more aromatic rings, generally each of 5 or 6 carbonatoms. Multiple aryl rings may be fused, as in naphthyl or unfused, asin biphenyl. The term “substituted aryl” refers to C5-C25 arylsubstituted with one or more lower C1-C10 alkyl, lower alkoxy, loweralkylthio, or lower dialkylamino. Exemplary aryl and substituted arylgroups include, for example, phenyl, benzyl, and the like. The term“alkoxy” refers to straight chain and branched C1-C25 alkoxy. The term“substituted alkoxy” refers to C1-C25 alkoxy substituted with one ormore lower C1-C10 alkyl, lower alkoxy, lower alkylthio, or lowerdialkylamino. The terms “heteroaryl” and “substituted heteroaryl” referto aryl and substituted aryl as defined above which can include one tofour heteroatoms, like oxygen, sulfur, or nitrogen or a combinationthereof, which heteroaryl group is optionally substituted at carbonand/or nitrogen atom(s) with the groups such as noted above. The terms“heterocycloalkyl” and “substituted heterocycloalkyl” refer tocycloalkyl and substituted cycloalkyl as defined above having one ormore rings of 5, 6 or 7 atoms with or without saturation or aromaticcharacter and at least one ring atom which is not carbon. Exemplaryheteroatoms include sulfur, oxygen, and nitrogen. Multiple rings may befused or unfused.

[0050] The initiators of the invention are derived fromomega-tertiary-amino-1-haloalkanes and mixtures thereof of the followinggeneral structures:

[0051] wherein X is halogen, preferably chlorine or bromine; and Z, R¹and R² are as defined above. In the process, selectedomega-tertiary-amino-1-haloalkanes, which alkyl groups contain 3 to 25carbon atoms, are reacted with an alkali metal typically at atemperature between about 35° C. and about 130° C., preferably at thereflux temperature of an alkane, cycloalkane, or aromatic reactionsolvent containing 5 to 12 carbon atoms and mixtures of such solvents.The resultant compound is a protected monofunctional organoalkali metalinitiator that is not chain extended having the formula

[0052] Tertiary amino-1-haloalkane raw materials (precursors) useful inthe practice of this invention are commercially available or can besynthesized using commercially available compounds. For example, theprecursor tertiary amino-1-haloalkanes can be prepared by the reactionof the corresponding amine with an alpha, omega dihalide, such as1-bromo-3-chloro-propane or 1,6-dichloro-hexane. This synthetic methodwas originally described by J. Almena, F. Foubelo, and M. Yus,Tetrahedron, 51, 11883-11890 (1995). In this regard, substantially 1:1molar ratios of the amine and dihaloalkane can be reacted in an inert ornon-polar solvent, such as cyclohexane, optionally in the presence of aphase transfer catalyst, followed by addition of NaOH.

[0053] A variation of this chemistry was recently disclosed inco-pending application Ser. No. 08/882,513 (Docket 6055, filed Jun. 25,1997), the entire disclosure of which is hereby incorporated byreference. See equation below:

[0054] In this procedure, an excess of the amine starting material wasreacted with an alpha, omega dihalide, such as 1-bromo-3-chloro-propaneor 1,6-dichloro-hexane. The excess amine served as an acid scavenger forthe acid liberated in the reaction. Each of these procedures affordedthe desired precursor molecules in high yield, and in high purity. Theprecursors could be purified, if desired, by conventional techniques,such as chromatography, distillation, or recrystallization. Typically,the precursors could be employed directly in the subsequent metallationreaction.

[0055] Compounds in which R¹ and R² together with the nitrogen atom towhich they are attached form

[0056] wherein y and R¹¹ are as defined above can also be prepared usinga dihalo substrate

[0057] wherein each X is independently halo, and preferably each X isbromide. Such substrates are commercially available or can be preparedusing known techniques. This dihalo substrate is reacted with thecorresponding amine generally represented by the formula NH₂-Z-X, inwhich X is also halo and preferably Cl, and Z is as defined above (forexample, —(CH₂)₃—), to prepare the halo amine precursor

[0058] Amines NH₂-Z-X are also commercially available or can besynthesized using known techniques.

[0059] Examples of tertiary amino-1-haloalkanes raw materials(precursors) useful in the practice of this invention include, but arenot limited to, 3-[(N-benzyl-N-methyl)amino]-1-propylhalide,3-[(N,N-dibenzyl)amino]-1-propylhalide,3-[(N-tert-butyl-N-methyl)amino]-1-propylhalide,3-[(N,N-di-tert-butyl)amino]-1-propylhalide,3-[(N-allyl-N-methyl)amino]-1-propylhalide,3-[(N,N-diallyl)amino]-1-propylhalide,2-methyl-3-[(N-benzyl-N-methyl)amino]-1-propylhalide,2-methyl-3-[(N,N-dibenzyl)amino]-1-propylhalide,2-methyl-3-[(N-tert-butyl-N-methyl)amino]-1-propylhalide,2-methyl-3-[(N,N-di-tert-butyl)amino]-1-propylhalide,2-methyl-3-[(N-allyl-N-methyl)amino]-1-propylhalide,2-methyl-3-[(N,N-diallyl)amino]-1-propylhalide,2,2-dimethyl-3-[(N-benzyl-N-methyl)amino]-1-propylhalide,2,2-dimethyl-3-[(N,N-dibenzyl)amino]-1-propylhalide,2,2-dimethyl-3-[(N-tert-butyl-N-methyl)amino]-1-propylhalide,2,2-dimethyl-3-[(N,N-di-tert-butyl)amino]-1-propylhalide,2,2-dimethyl-3-[(N-allyl-N-methyl)amino]-1-propylhalide,2,2-dimethyl-3-[(N,N-diallyl)amino]-1-propylhalide,4-[(N-benzyl-N-methyl)amino]-1-butylhalide,4-[(N,N-dibenzyl)amino]-1-butylhalide,4-[(N-tert-butyl-N-methyl)amino]-1-butylhalide,4-[(N,N-di-tert-butyl)amino]-1-butylhalide,4-[(N-allyl-N-methyl)amino]-1-butylhalide,4-[(N,N-diallyl)amino]-1-butylhalide,6-[(N-benzyl-N-methyl)amino]-1-hexylhalide,6-[(N,N-dibenzyl)amino]-1-hexylhalide,6-[(N-tert-butyl-N-methyl)amino]-1-hexylhalide,6-[(N,N-di-tert-butyl)amino]-1-hexylhalide,6-[(N-allyl-N-methyl)amino]-1-hexylhalide,6-[(N,N-diallyl)amino]-1-hexylhalide,8-[(N-benzyl-N-methyl)amino]-1-octylhalide,8-[(N,N-dibenzyl)amino]-1-octylhalide,8-[(N-tert-butyl-N-methyl)amino]-1-octylhalide,8-[(N,N-di-tert-butyl)amino]-1-octylhalide,8-[(N-allyl-N-methyl)amino]-1-octylhalide,8-[(N,N-diallyl)amino]-1-octylhalide, 3-[(N-methyl-N-C2-C25 alkyl orsubstituted alkyl)amino]-1-propylhalide, 2-methyl-3-[(N-methyl-N-C2-C25alkyl or substituted alkyl)amino]-1-propylhalide,2,2-dimethyl-3-[(N-methyl-N-C2-C25 alkyl or substitutedalkyl)amino]-1-propylhalide, 4-[(N-methyl-N-C2-C25 alkyl or substitutedalkyl)amino]-1-butylhalide, 6-[(N-methyl-N-C2-C25 alkyl or substitutedalkyl)amino]-1-hexylhalide, 8-[(N-methyl-N-C2-C25 alkyl or substitutedalkyl)amino]-1-octylhalide, 3-[(N-methyl-N-C5-C25 aryl or substitutedaryl)amino]-1-propylhalide, 2-methyl-3-[(N-methyl-N-C5-C25 aryl orsubstituted aryl)amino]-1-propylhalide,2,2-dimethyl-3-[(N-methyl-N-C5-C25 aryl or substitutedaryl)amino]-1-propylhalide, 4-[(N-methyl-N-C5-C25 aryl or substitutedaryl)amino]-1-butylhalide, 6-[(N-methyl-N-C5-C25 aryl or substitutedaryl)amino]-1-hexylhalide, 8-[(N-methyl-N-C5-C25 aryl or substitutedaryl)amino]-1-octylhalide, and the like and mixtures thereof. The halo-or halide group is selected from chlorine and bromine.

[0060] The alkali metal used in preparing the organometallic compoundscontaining tertiary amines, selected from lithium, sodium and potassium,is used as a dispersion whose particle size usually does not exceedabout 300 microns. Preferably the particle size is between 10 and 300microns although coarser particle size alkali metal can be used. Whenlithium metal is employed, the lithium metal can contain 0.2 to 5.0 andpreferably 0.8 weight percent sodium. The alkali metal is used inamounts of 90% of theoretical to a 400% excess above the theoreticalamount necessary to produce the compounds. The reaction temperature isgreater than about 35° C. up to just below the decomposition of thereactants and/or the product. An abrasive can be optionally added toimprove the metallation reaction. The yields of tertiary aminoorganometallic compounds prepared by this invention typically exceed85%.

[0061] The organoalkali metal initiators of the formulae

[0062] in which n is from greater than 0 to 5 are prepared by reacting acompound of the formulae

[0063] wherein M, Z, R¹, and R² have the meanings ascribed above, withone or more unsaturated organic compounds, such as one or moreconjugated diene hydrocarbons, one or more alkenylsubstituted aromaticcompounds, or mixtures of one or more dienes with one or morealkenylsubstituted aromatic compounds, to form an extended hydrocarbonchain between M and Z, which extended chain is denoted as Q_(n). Thenon-chain extended initiator is reacted with a one or more conjugateddiene hydrocarbons, one or more alkenylsubstituted aromatic compounds,or mixtures of one or more dienes with one or more alkenylsubstitutedaromatic compounds, advantageously in a predominantly alkane,cycloalkane, or aromatic reaction solvent of 5 to 10 carbon atoms, andmixtures of such solvents, to produce a monofunctional initiator with anextended chain or tether between the metal atom M and Z and mixturesthereof with the non-chain extended compounds. The chain extensionreaction can be performed in several different manifolds.

[0064] In one embodiment, a dilute solution of the non-chain extendedinitiator can be separated from solid excess alkali metal and co-productalkali metal halide (for example, the excess lithium metal and lithiumchloride by-product when a lithium metal dispersion is used). The chainextension agent can then be added to the solution to increase thesolubility of the non-chain extended initiator. Optionally, theconcentration can be adjusted by removal of at least a portion of thesolvent. In another embodiment, the chain extension agent is added tothe reaction mixture prior to filtration to remove the excess alkalimetal and co-product alkali metal halide.

[0065] The chain extension can be carried out under a variety ofconditions. Generally the chain extension reaction can be conducted attemperatures ranging from about −30° C. to about 150° C. The chainextension may also be conducted in the presence of certain Lewis bases,generally at temperatures sufficient to slow down polymerization,relative to chain extension. In this aspect of the invention, the Lewisbase may be one or more ethers, advantageously one or more aliphaticethers, such as but not limited to diethyl ether, dimethyl ether, methyltertiary butyl ether (MTBE), tetrahydrofuran (THF),2-methyltetrahydrofuran, and the like and mixtures thereof. The Lewisbase may also be one or more tertiary amines, such as aliphatic aminesselected from the group consisting of trimethylamine, triethylamine,dimethylbutylamine, N,N,N′,N′-tetramethylethylenediamine (TMEDA), andthe like as well as mixtures thereof. The proportion of these Lewisbases to the organometallic being chain extended may be varied fromabout 0.05 mole to about 5.0 moles per mole of organometallic. Thereaction temperature used in the presence of the Lewis base may belowered to about −30° C. to about +30° C. to prevent attack by theorganometallic on the Lewis base. As the skilled artisan willappreciate, however, the process conditions can depend on variousfactors such as the nature of Lewis base, the nature of theorganometallic, and the ratio of the Lewis base to the organometallic,and can vary from the ranges given above.

[0066] In addition, as noted above, the chain extension reaction can becarried out either prior to isolation of the organometallic species fromthe solid excess alkali metal and co-product alkali metal halide, orsubsequent to the filtration. It is noted that not all of the initiatormust be chain extended, and the mixtures of chain extended and non-chainextended initiators can also provide benefits. It is also noted thatless than one equivalent chain extension (i.e., n is greater than 0 butless than 1) can still provide hydrocarbon solubility and iscontemplated to be within the scope of this invention.

[0067] The unsaturated organic chain extending compounds used inproducing the initiators of this invention are chosen from the group oforganic compounds that can be polymerized anionically in a reactioninitiated by an alkali metal or its carbanionic derivative. Preferredare conjugated dienes and alkenyl substituted aromatic compounds, butother compounds can also be used in accordance with the presentinvention so long as the compound can form a chain extension.

[0068] Exemplary conjugated diene hydrocarbons include, but are notlimited to, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene,1,3-pentadiene (piperylene), myrcene, 2-methyl-3-ethyl-1,3-butadiene,2-methyl-3-ethyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene,1,3-heptadiene, 3-methyl-1,3-heptadiene, 1,3-octadiene,3-butyl-1,3-octadiene, 3,4-dimethyl-1,3-hexadiene,3-n-propyl-1,3-pentadiene, 4,5-diethyl-1,3-octadiene,2,4-diethyl-1,3-butadiene, 2,3-di-n-propyl-1,3-butadiene,2-methyl-3-isopropyl-1,3-butadiene, and the like and mixtures thereof.Other conjugated diene hydrocarbons can also be useful in practicingthis invention, such as those disclosed in U.S. Pat. No. 3,377,404.

[0069] The polymerizable alkenylsubstituted aromatic hydrocarbons usefulin producing the chain extended initiators of this invention include,but are not limited to, styrene, alpha-methylstyrene, vinyltoluene,2-vinylpyridine, 4-vinylpyridine, 1-vinylnaphthalene,2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene,2-alpha-methylvinylnaphathalene, 1,2-diphenyl-4-methyl-1-hexene, and thelike and mixtures of these, as well as alkyl, cycloalkyl, aryl, alkaryland aralkyl derivatives thereof in which the total number of carbonatoms in the combined hydrocarbon constituents is generally not greaterthan 18. Examples of these latter compounds include without limitation3-methylstyrene, 3,5-diethylstyrene, 2-ethyl-4-benzylstyrene,4-phenylstyrene, 4-p-tolylstyrene, 2,4-divinyltoluene,4,5-dimethyl-1-vinylnaphthalene, and the like and mixtures thereof.Reference is made to U.S. Pat. No. 3,377,404 for disclosure ofadditional alkenyl substituted aromatic compounds. Non-polymerizableconjugated dienes and alkenyl substituted aromatic compounds includingbut not limited to 1,1-diphenylethylene and 2,4-hexadiene may also beemployed as chain extension agents in accordance with the presentinvention.

[0070] The inert solvent employed during the preparation of theinitiators of the present invention, or in subsequent polymerizations asdiscussed in more detail below, for some applications is preferably anon-polar solvent such as a hydrocarbon, since anionic polymerization inthe presence of such non-polar solvents is known to produce polyeneswith high 1,4-contents from 1,3-dienes. Inert hydrocarbon solventsuseful in practicing this invention include but are not limited to inertliquid alkanes, cycloalkanes, aromatic solvents and mixtures thereof.Exemplary alkanes and cycloalkanes can contain five to ten carbon atoms,such as but not limited to pentane, hexane, cyclohexane,methylcyclohexane, heptane, methylcycloheptane, octane, decane and thelike as well as mixtures thereof. Exemplary aromatic solvents cancontain six to ten carbon atoms, such as but not limited to benzene,toluene, ethylbenzene, p-xylene, m-xylene, o-xylene, n-propylbenzene,isopropylbenzene, n-butylbenzene, and the like, and mixtures thereof.

[0071] While the compounds have been described herein as useful asanionic polymerization initiators, it is noted that the compounds of theinvention as not so limited in use and can also be useful as reagents ina variety of synthesis applications.

[0072] The present invention also provides a process for the anionicpolymerization of anionically polymerizable monomers. The process of theinvention includes the step of initiating polymerization of one or moremonomers or compounds that can be anionically polymerized. Exemplaryanionically polymerizable compounds include conjugated diene hydrocarbonmonomers, a mixture of conjugated diene monomers, alkenyl substitutedaromatic compounds, a mixture of alkenyl substituted aromatic compounds,or a mixture of one or more conjugated diene hydrocarbons and one ormore alkenyl substituted aromatic compounds.

[0073] Other anionically polymerizable compounds can also be used asknown in the art, singly or in combination with one another or withother types of monomer(s). For example, the monomers can include one ormore polar monomers such as, without limitation, esters, amides, andnitriles of acrylic and methacrylic acid, and mixtures thereof with oneanother and/or with other monomers. Examples of polar monomers includewithout limitation methyl methacrylate, methyl acrylate, t-butylmethacrylate, t-butyl acrylate, ethyl methacrylate,N,N-dimethylacrylamide, lauryl methacrylate, stearyl methacrylate,2,3-epoxypropyl methacrylate, decyl methacrylate, and octylmethacrylate. For reference, see Macromolecules, 14, 1599 (1981);Polymer 31, 106 (1990); Polymer, 34, 2875 (1993). See also U.S. Pat. No.5,900,464.

[0074] The polymers of the invention can also include silicone block(s).Such blocks can be prepared by anionically polymerizing one or morecyclic siloxane monomers as known in the art. See U.S. Pat. No.6,020,430. Generally such monomers can be defined by the formula(R¹R²SiO)_(y), wherein R¹ and R² are each independently selected fromthe group consisting of hydrogen, alkyl, substituted alkyl, alkenyl,substituted alkenyl, aryl, and substituted aryl and y=3-10.

[0075] Additional anionically polymerizable monomers include olefinssuch as ethylene, porpylene, and the like. See U.S. Pat. No. 5,849,847.

[0076] The monomer(s) are polymerized in a hydrocarbon or mixedhydrocarbon-polar solvent medium generally at a temperature of 10° C. to150° C. with one or more initiators having the formula:

[0077] wherein R¹, R², Z, Q, n and M are as defined above. This providesan intermediate living polymer of the formula:

[0078] wherein:

[0079] P is a saturated or unsaturated hydrocarbyl group derived byincorporation of one or more anionically polymerizable compounds, suchas but not limited to, one or more compounds selected from the groupconsisting of conjugated diene hydrocarbons, alkenylsubstituted aromaticcompounds, and mixtures thereof;

[0080] m is from 2 to 20,000; and

[0081] M, Q, Z, R¹, R², and n have the meanings ascribed above.

[0082] The intermediate living polymer is then reacted with a suitableprotonating, functionalizing, or coupling or linking agent, as known inthe art.

[0083] In one aspect of the invention, the living polymer is reactedwith a functionalizing agent (or electrophile) of the formula

X—Y-T-(A-R⁴R⁵R⁶)_(k)

[0084] wherein:

[0085] X is halide selected from the group consisting of chloride,bromide and iodide;

[0086] Y is a branched or straight chain hydrocarbon connecting groupwhich contains 1-25 carbon atoms, optionally substituted with aryl orsubstituted aryl;

[0087] T is selected from the group consisting of oxygen, sulfur, andnitrogen and mixtures thereof;

[0088] A is an element selected from Group IVa of the Periodic Table ofthe Elements;

[0089] R⁴, R⁵, and R⁶ are each independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, aryl, substitutedaryl, cycloalkyl, and substituted cycloalkyl, or R⁶ is optionally a—(CR⁷R⁸)_(l)— group linking two A when k is 2, wherein R⁷ and R⁸ areeach independently selected from the group consisting of hydrogen,alkyl, substituted alkyl, aryl, substituted aryl, cycloalkyl, andsubstituted cycloalkyl, and l is an integer from 1 to 7; and

[0090] k is 1 when T is oxygen or sulfur, and 2 when T is nitrogen. Thusthe skilled artisan will appreciate that R⁶ as used herein includes thegroup

[0091]  linking two A groups when k is 2.

[0092] The functionalizing agents can be prepared as described, forexample, in International Publication WO 97/16465, the entire disclosureof which is incorporated by reference. In addition, the electrophilescan be prepared as described in K. Ueda, A. Hirao, and S. Nakahama,Macromolecules, 23, 939 (1990); U.S. Pat. No. 5,496,940; U.S. Pat. No.5,600,021; U.S. Pat. No. 5,362,699; A. Alexakis, M. Gardette, and S.Colin, Tetrahedron Letters, 29, 1988, 2951; B. Figadere, X. Franck, andA. Cave, Tetrahedron Letters, 34, 1993, 5893; J. Almena, F. Foubelo, andM. Yus, Tetrahedron, 51, 1995, 11883; D. F. Taber and Y. Wang, J. Org.Chem., 58, 1993, 6470; F. D. Toste and I. W. J. Still, Synlett, 1995,159; and U.S. Pat. No. 5,493,044. The functionalization step can beconducted at temperatures ranging from about −30° C. to about 150° C.

[0093] Other compounds useful in functionalizing living polymersinclude, but are not limited to, alkylene oxides, such as ethyleneoxide, propylene oxide, styrene oxide, and oxetane; oxygen; sulfur;carbon dioxide; halogens such as chlorine, bromine and iodine; propargylhalides; alkenylhalosilanes and omega-alkenylarylhalosilanes, such asstyrenyldimethyl chlorosilane; sulfonated compounds, such as 1,3-propanesultone; amides, including cyclic amides, such as caprolactam,N-benzylidene trimethylsilylamide, and dimethyl formamide; siliconacetals; 1,5-diazabicyclo[3.1.0]hexane; allyl halides, such as allylbromide and allyl chloride; methacryloyl chloride; amines, includingprimary, secondary, tertiary and cyclic amines, such as3-(dimethylamino)-propyl chloride andN-(benzylidene)trimethylsilylamine; haloalkyltrialkoxysilanes;epihalohydrins, such as epichlorohydrin, epibromohydrin, andepiiodohydrin, and other materials as known in the art to be useful forterminating or end capping polymers. These and other usefulfunctionalizing agents are described, for example, in U.S. Pat. Nos.3,786,116 and 4,409,357, the entire disclosure of each of which isincorporated herein by reference.

[0094] Other particularly advantageous functionalizing agents areimines. Imines are generally known in the art and can be described ashaving the general formula:

[0095] wherein each R¹⁰ is independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, aryl, substitutedaryl, cycloalkyl, substituted cycloalkyl, alkoxy, substituted alkoxy,heteroaryl, substituted heteroaryl, heterocycloalkyl, substitutedheterocycloalkyl, and alkylsilyl (such as trimethylsilyl). Exemplaryimine functionalizing agents include without limitationN-(benzylidene)trimethylsilylamine

[0096] (in which TMS is trimethylsilyl and Ph is phenyl); andN-(benzylidene)methylamine

[0097] Examples of difunctional coupling agents useful to form protectedtelechelic polymers include, but are not limited to, Me₂SiCl₂,Me₂Si(OMe)₂, Me₂SnCl₂, Ph₂SiCl₂, MePhSiCl₂, ClMe₂SiCH₂CH₂SiMe₂Cl, andMe₂SiBr₂, and the like and mixtures thereof.

[0098] Examples of useful multifunctional linking or coupling agentsinclude isomeric (mixtures of ortho, meta and para) dialkenylaryls andisomeric di- and trivinylaryls, such as 1,2-divinylbenzene,1,3-divinylbenzene, 1,4-divinylbenzene, 1,2,4-trivinylbenzenes,1,3-divinylnaphthalenes, 1,8-divinylnaphthalene,1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene,1,4-diisopropenylbenzene, 1,3,5-trivinylnaphthalene, and other suitablematerials known in the art to be useful for coupling polymers, as wellas mixtures of coupling agents. Other exemplary multifunctional linkingor coupling agents include halosilanes, halostannanes, phosphorushalides, and the like and mixtures thereof. Examples of the same includewithout limitation tin tetrachloride (SnCl₄), silicon tetrachloride(SiCl₄), methyl trichlorosilane (MeSiCl₃), HSi(OMe)₃, Si(OEt)₄,Cl₃SiSiCl₃, phosphorus trichloride and the like and mixtures thereof.See also U.S. Pat. Nos. 3,639,517 and 5,489,649, and R. P. Zelinski etal in J. Polym. Sci., A3, 93, (1965) for these and additional couplingagents. Mixtures of coupling agents can also be used. Generally, theamount of coupling agent used is such that the molar ratio of protectedliving polymer anions to coupling agents ranges from 1:1 to 24:1. Thislinking process is described, for example, in U.S. Pat. No. 4,409,357and by L. J. Fetters in Macromolecules, 9,732 (1976).

[0099] The resultant polymer thus can be a linear, homotelechelic,heterotelechelic, branched, or radial polymer having one or moreterminal tertiary amino functional groups. The polymer can be recoveredfrom the reaction media and optionally hydrogenated and/or deprotected.

[0100] If a mixture of monomers is employed in the polymerization, themonomers can be added together to afford random or tapered blockcopolymers. The monomers can also be charged to the reactor sequentiallyto afford block copolymers.

[0101] Monomer(s) to be anionically polymerized to form living polymeranions can be selected from any suitable monomer capable of anionicpolymerization, including conjugated alkadienes, alkenylsubstitutedaromatic hydrocarbons, and mixtures thereof. Examples of suitableconjugated alkadienes include, but are not limited to, 1,3-butadiene,isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, myrcene,2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-pentadiene,1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3-heptadiene,3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene,3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-pentadiene,4,5-diethyl-1,3-octadiene, 2,4-diethyl-1,3-butadiene,2,3-di-n-propyl-1,3-butadiene, and 2-methyl-3-isopropyl-1,3-butadiene.

[0102] Examples of polymerizable alkenylsubstituted aromatichydrocarbons include, but are not limited to, styrene,alpha-methylstyrene, vinyltoluene, 2-vinylpyridine, 4-vinylpyridine,1-vinylnaphthalene, 2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene,2-alpha-methylvinylnaphthalene, 1,2-diphenyl-4-methyl-1-hexene andmixtures of these, as well as alkyl, cycloalkyl, aryl, alkylaryl andarylalkyl derivatives thereof in which the total number of carbon atomsin the combined hydrocarbon constituents is generally not greater than18. Examples of these latter compounds include 3-methylstyrene,3,5-diethylstyrene, 4-tert-butylstyrene, 2-ethyl-4-benzylstyrene,4-phenylstyrene, 4-p-tolylstyrene, 2,4-divinyltoluene and4,5-dimethyl-1-vinylnaphthalene. U.S. Pat. No. 3,377,404, incorporatedherein by reference in its entirety, discloses suitable additionalalkenylsubstituted aromatic compounds.

[0103] The inert solvent is preferably a non-polar solvent such as ahydrocarbon, since anionic polymerization in the presence of suchnon-polar solvents is known to produce polyenes with high 1,4-contentsfrom 1,3-dienes. Inert hydrocarbon solvents useful in practicing thisinvention include but are not limited to inert liquid alkanes,cycloalkanes and aromatic solvents and mixtures thereof. Exemplaryalkanes and cycloalkanes include those containing five to 10 carbonatoms, such as pentane, hexane, cyclohexane, methylcyclohexane, heptane,methylcycloheptane, octane, decane and the like and mixtures thereof.Exemplary aryl solvents include those containing six to ten carbonatoms, such as toluene, ethylbenzene, p-xylene, m-xylene, o-xylene,n-propylbenzene, isopropylbenzene, n-butylbenzene, and the like andmixtures thereof.

[0104] Polar solvents (modifiers), however, can be added to thepolymerization reaction to alter the microstructure of the resultingpolymer, i.e., increase the proportion of 1,2 (vinyl) microstructure orto promote functionalization or randomization. For certain applications,it can be advantageous to provide polymers having from 20 to 80% 1,2vinyl microstructure. Examples of polar modifiers include, but are notlimited to: diethyl ether, dibutyl ether, tetrahydrofuran (THF),2-methyltetrahydrofuran, methyl tert-butyl ether (MTBE),diazabicyclo[2.2.2]octane (DABCO), triethylamine, tri-n-butylamine,N,N,N′,N′-tetramethylethylenediamine (TMEDA), and 1,2-dimethoxyethane(glyme). The amount of the polar modifier added depends on the vinylcontent desired, the nature of the monomer, the temperature of thepolymerization, and the identity of the polar modifier. The polarsolvent (modifier) can be added to the reaction medium at the beginningof the polymerization as part of the solvent reaction medium, addedduring the polymerization or after polymerization but prior tofunctionalization or coupling.

[0105] Unsaturation in the polymer chain may be treated as known in theart to modify the same. For example, the unsaturated polymer may bereacted with one or more epoxides to form one or more epoxy groups alongthe backbone thereof.

[0106] The polymers produced may be optionally hydrogenated to affordadditional novel, functionalized polymers. Examples of methods tohydrogenate the polymers of this invention are described in Falk,Journal of Polymer Science: Part A-1, vol. 9, 2617-2623 (1971), Falk,Die Angewandte Chemie, 21, 17-23 (1972), U.S. Pat. Nos. 4,970,254,5,166,277, 5,393,843, 5,496,898, and 5,717,035. The hydrogenation of thefunctionalized polymer is conducted in situ, or in a suitable solvent,such as hexane, cyclohexane or heptane. This solution is contacted withhydrogen gas in the presence of a catalyst, such as a nickel catalyst.The hydrogenation is typically performed at temperatures from 25° C. to150° C., with an archetypal hydrogen pressure of 15 psig to 1000 psig.The progress of this hydrogenation can be monitored by InfraRed (IR)spectroscopy or Nuclear Magnetic Resonance (NMR) spectroscopy. Thehydrogenation reaction can be conducted until at least 90% of thealiphatic unsaturation has been saturated. The hydrogenated functionalpolymer is then recovered by conventional procedures, such as removal ofthe catalyst with aqueous acid wash, followed by solvent removal orprecipitation of the polymer.

[0107] The protecting group can be removed from the functionalizedpolymer, if desired. This deprotection can be conducted either prior toor subsequent to the optional hydrogenation of the aliphaticunsaturation. Deprotection of these polymers affords a linear or radialpolymer which contain either a mono-, di- or multifunctional terminalprimary or secondary amino group.

[0108] When the protecting group R¹ (and optionally R²) is aralkyl, andpreferably benzyl or benzyl derivative, then deprotection andhydrogenation can be performed concurrently. In this aspect of theinvention, the polymer can be partially hydrogenated under conditionsselected to leave the benzyl or benzyl derived protecting group intact.Alternatively the polymer can be partially hydrogenated so as to removethe benzyl or benzyl derived protecting group, yet substantiallyhydrogenate unsaturation in the polymer chain.

[0109] Various methods can be employed for the removal of the othertertiary alkyl, such as tertiary butyl, allyl, or methyl protectinggroups. For example, to remove tert-alkyl-protecting groups, theprotected polymer is mixed with Amberlyst^(□) 15 ion exchange resin andheated at an elevated temperature, for example 150° C., untildeprotection is complete. In addition, tert-alkyl-protecting groups canalso be removed by reaction of the polymer with trifluoroacetic acid, ortrimethylsilyliodide. Additional methods of deprotection of thetert-alkyl protecting groups can be found in T. W. Greene and P. G. M.Wuts, Protective Groups in Organic Synthesis, 3d Edition, Wiley, NewYork, 1999, page 574. See also U.S. Pat. No. 5,922,810, issued Jul. 13,1999.

[0110] As noted above, aralkyl, such as benzyl and benzyl derivedprotecting groups, can be removed under conditions used to hydrogenatepolymers. See T. W. Greene and P. G. M. Wuts, Protective Groups inOrganic Synthesis, 3d Edition, Wiley, New York, 1999, pages 577-585 forthis and other deprotection techniques for aralkyl protecting groups.Hydrogenation may also be used to remove the protecting group

[0111] as defined above to liberate the nitrogen atom. It is noted thathydrogenation conditions can be selected so as to partially hydrogenatethe polymer and leave the aralkyl, for example benzyl or benzylderivative, intact.

[0112] The allyl protecting group can be removed utilizing a rhodiumcatalyst. See B. C. Laguzza and B. Ganem, Tetrahedron Lett., 22, 1483(1981). Reference is also made to T. W. Greene and P. G. M. Wuts,Protective Groups in Organic Synthesis, 3d Edition, Wiley, New York,1999, pages 574-76.

[0113] Methyl protecting groups can be removed photochemically. Forexample, the methyl protecting groups can be cleaved or removedphotochemically in the presence of an electron acceptor such as9,10-dicyanoanthracene. J. Santamaria, R. Ouchabane, and J. Rigaudy,Tetrahedron Lett., 30, 2927 (1989). Reference is also made to T. W.Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, 3dEdition, Wiley, New York, 1999, pages 573-74.

[0114] After deprotection, the degree of functionality of the aminopolymer can be determined by the method of J. S. Fritz and G. H. Schenk,Quantitative Analytical Chemistry, 3rd edition; Allyn and Bacon, Inc.:Boston, 1974, p. 1974. The polymer was dissolved in a 1/1 mixture ofchloroform and glacial acetic acid, and titrated with perchloric acid,and with methyl violet as the indicator. The deprotection is generallynear quantitative to provide an amine functionality of about I, or whena protected amine functionalized electrophile is used, about 2 forlinear polymers.

[0115] The resultant polymer can be a linear monofunctional polymer(resulting from quench of the living polymer with a protonating agent).The polymer can also be a linear telechelic polymer having two protectedfunctional groups, in which the protecting group(s) and/or protectedfunctionalities can be the same or different. Polymers possessingsimilarly protected functional groups can be deprotected by selecting areagent specifically suited to remove the similar protecting groups.Alternatively, the invention also provides a process for the preparationof a linear polymer possessing one free telechelically functional groupand one protected telechelically functional group. In this aspect of theinvention, one type of protecting group is selectively deprotected froma dissimilarly protected functionality on the end(s) of the arms of thelinear polymer chains, produced as described above, using selectivereagents specifically suited to remove the targeted protective group andliberate the desired functionality, on the end of the polymer chain.

[0116] In yet another aspect of the invention, star or multi-branchedpolymers are produced by linking the living polymer anions using acoupling or linking agent as known in the art (for example themultifunctional linking agents as described above). The star polymerscan be prepared using the protected amine initiators of the presentinvention and mixtures of these initiators with one another as well aswith other protected functionalized initiators having differentprotecting groups and/or different protected functionalities. See, forexample, U.S. Pat. Nos. 5,527,753, 5,827,929; 5,821,307;5,919,870;5,798,418; and 5,780,551, for a discussion of variousprotected functionalized initiators and star or multi-branched polymersmade using various initiators. In addition, other types of protectedfunctionalized initiators and/or non-functional initiators as known inthe art can also be used in combination with the initiators of thepresent invention. The resultant polymers can have 3 to 30 arms. Theprotecting groups of the arms of the resultant star polymers can beremoved, as discussed above, including the selective deprotection ofdissimilar protecting groups.

[0117] The following table details experimental conditions that willselectively remove one of the protecting groups (more labile) from thepolymer, while retaining the other protecting group (more stable).LABILE STABLE CONDITIONS t-Butyldimethylsilyl t-Butyl Tetrabutylammoniumfluoride t-Butyldimethylsilyl t-Butyl 1 N HCl t-ButyldimethylsilylDialkylamino Tetrabutylammonium fluoride t-ButyldimethylsilylDialkylamino 1 N HCl t-Butyl Dialkylamino Amberlyst ® resin t-AmylDialkylamino Amberlyst ® resin Trimethylsilyl t-Butyl Tetrabutylammoniumfluoride Trimethylsilyl t-Butyl 1 N HCl Trimethylsilyl DialkylaminoTetrabutylammonium fluoride Trimethylsilyl Dialkylamino 1 N HCl2,2,5,5-Tetramethyl-2,5- t-Butyl Tetrabutylammonium Fluoridedisila-1-azacyclopentane 2,2,5,5-Tetramethyl-2,5- t-Butyl 1 N HCldisila-1-azacyclopentane 2,2,5,5-Tetramethyl-2,5- DialkylaminoTetrabutylammonium Fluoride disila-1-azacyclopentane2,2,5,5-Tetramethyl-2,5- Dialkylamino 1 N HCl disila-1-azacyclopentane

[0118] In another aspect of this invention, unique polymers produced bythe process described above are provided. The polymers produced by thisprocess may have linear, branched or radial architecture. Further, thepolymers may be monofunctional (produced by quench of the living anion),homotelechelic (for example, produced by coupling of the living anionwith a coupling agent with two active sites or by trapping of the livingpolymer anion with a protected, functionalized electrophileelectrophile), heterotelechelic (produced by quench of the livingpolymer anion with an electrophile), or polyfunctional (produced bycoupling of the living anion with a coupling agent with more than twoactive sites, such as tin tetrachloride or diisopropenylbenzene).

[0119] For example, exemplary monofunctional and telechelic polymers ofthe invention are represented by the formulas below:

[0120] wherein:

[0121] Q, Z, R¹, R², and n have the meanings ascribed above;

[0122] P is a saturated or unsaturated hydrocarbyl group derived byincorporation of one or more anionically polymerizable compounds, suchas but not limited to compounds selected from the group consisting ofconjugated dienes, alkenylsubstituted aromatic hydrocarbons and mixturesthereof;

[0123] m is from 2 to 20,000; and

[0124] FG is hydrogen or a protected or unprotected functional group.Alternatively, FG can be a polymer segment derived by reaction of afunctional group with at least one comonomer.

[0125] The skilled artisan will appreciate that monofunctional polymersresult when FG is hydrogen, produced by quench of the living anion. Theresultant mono-functionalized polymer can be treated to remove one ofthe protecting groups (when R¹ and R² are not the same) or to removeboth protecting groups in one step (for example when R¹ and R² are thesame) or sequentially (when R¹ and R² are not the same and are removedunder different conditions). Removing one protecting group provides analpha secondary amine functionalized polymer of the formula

[0126] while removing both protecting groups (either simultaneously orsequentially) provides an alpha primary amine functionalized polymer ofthe formula

H₂N-Z-Qn-Pm-FG

[0127] The skilled artisan will appreciate that FG can also be aprotected or non-protected functional group or a polymer segment derivedby incorporation of one or more comonomers with a functional group.

[0128] Telechelic polymers (both homotelechelic and heterotelechelic)can be prepared by reaction of the living polymer with any of the typesof functionalizing agents or electrophiles as known in the art describedin more detail above. For example, homotelechelic polymers can beproduced by trapping of the living polymer anion with a protected,functionalized electrophile. Heterotelechelic polymers include thosepolymers in which FG and the omega protected amine functionality aredifferent. In one aspect of the invention, heterotelechelic polymersinclude polymers which have been terminated using a functionalizingagent (or electrophile) of the formula X—Y-T-(A-R⁴R⁵R⁶)k wherein X, Y,T, A, R⁴, R⁵, R⁶ and k are the same as defined above. Exemplary polymersfunctionalized with such an electrophile can have the structure below:

[0129] wherein Y, Z, T, A, P, Q, k, m, n, R¹, R², R⁴, R⁵, and R⁶ are thesame ascribed above (i.e., FG is —Y-T-(A(R⁴R⁵R⁶)k). In one advantageousembodiment of the invention the polymer has the formula:

[0130] wherein Y, Z, P, Q, m, n, R¹, and R² are the same ascribed above.

[0131] The protected linear functionalized polymers can be treated toremove one, two or more protecting groups as described above. Theresultant deprotected functionalized polymers can have the followingstructures:

[0132] (removal of R¹ alone),

H₂N Z-Qn-Pm—Y-T(AR⁴R⁵R⁶)k

[0133] (simultaneous or sequential removal of R¹ and R²),

H₂N-Z-Qn-Pm—Y-T(H)k

[0134] (simultaneous or sequential removal of R¹, R² and —AR⁴R⁵R⁶),

[0135] (removal of —AR⁴R⁵R⁶), and

[0136] (removal of R¹ and —AR⁴R⁵R⁶).

[0137] In a particularly advantageous embodiment of the invention, thepolymer includes two R¹ protecting groups which are the same and bothR¹s are removed to provide an alpha, omega secondary diaminefunctionalized polymer of the formula

[0138] In another aspect of the invention, heterotelechelic polymersinclude polymers which have been terminated using an iminefunctionalizing agent (or electrophile) of the formula

[0139] wherein each R¹⁰ is as defined above. The resultant polymerfunctionalized with an imine electrophile can have the structure below:

[0140] wherein R¹, R², Z, Q, n, P, m, and R¹⁰ have the meanings as setforth above. One, two or more protecting groups can be removed in thisaspect of the invention as well.

[0141] One exemplary polymer of this aspect of the invention has theformula

[0142] wherein Ph is phenyl and Me is methyl. In this aspect of theinvention, when R¹ is methyl, the polymer can be treated remove bothmethyl groups to provide a diamine functionalized polymer having asecondary amine functionality and a primary amine functionality, i.e.,

[0143] When R¹ is not methyl, the polymers can be treated to selectivelyremove either the R¹ protecting group or the methyl group to providepolymers of the formula:

[0144] (remove —CH₃)

[0145] (remove R¹)

[0146] or

[0147] (remove R¹ and R², either simultaneously or sequentially).

[0148] Complete deprotection or removal of the protecting groupsprovides polymers of the formula

[0149] Another exemplary polymer in this aspect of the invention canhave the structure:

[0150] wherein TMS is trimethylsilyl. Again the various groups on theamine functionalities can be removed to provide polymers such as

[0151] (remove the TMS group);

[0152] (remove R¹); and

[0153] (remove both R¹ and R², either simultaneously or sequentially).

[0154] Also in this embodiment of the invention, it is noted that theliving polymer can be reacted with an imine and rather than isolatingthe resultant imine functionalized polymer as described above, anintermediate polymer of the formula

[0155] can be directed to an additional step in which the nitrogen atomis reacted with a suitable agent to form a polymer having to polymersegment or functionality as represented generally below:

[0156] in which X is a polymer segment or functionality derived byreaction of a suitable reagent with the imine intermediate and R¹⁰attached to the N atom may be present or absent depending upon thereaction. For example, the intermediate polymer can be reacted withdiisocyanate to form a polymer having at least one isocyanate group asillustrated below:

[0157] Particularly preferred polymers include polymers havingtelechelic primary and/or secondary amine groups, as well as theirhydrogenated analogs. A primary amine results when all protecting groupsare removed from a protected amine functionality. A secondary amineresults when one but not another protecting group is removed from aprotected amine functionality. The primary and secondary amine groupscan be represented generally by the formula —N(H)R, in which R ishydrogen (primary amine) or R² as defined above (secondary amine).

[0158] The newly liberated primary or secondary amino groups can thenparticipate in subsequent polymerization chemistry. For example, a monoprimary or secondary amine and/or a telechelic primary or secondarydiamine can react with a diisocyanate to afford a polyurethane.Advantageously the diisocyanate is a non-symmetrical diisocyanate, suchas isophorone diisocyanate, as shown below:

[0159] Preferably an excess amount of diisocyanate is used to minimizeor prevent chain extension. After the diisocynate is reacted with theamine terminated polymer, the isocyanate groups on the terminal ends ofthe polymer may be blocked. This allows the polymers to be used informulations with diols and other groups which normally react withisocyanates, such as coating systems either in solvents or aqueoussystems. See U.S. Pat. No. 5,710,209.

[0160] The newly liberated primary or secondary amino groups can alsoreact with an unreacted epoxy group (oxirane) groups to form partiallyor fully crosslinked epoxy resins. Similar to the diisocyanates,advantageously an unsymmetrical diepoxide reagent is used in excessamounts to minimize or prevent chain extension. An exemplaryunsymmetrical diepoxide is

[0161] However, any diepoxide can be used, such as the diglycidyl etherof Bisphenol A (DGEBA). Other aromatic epoxies can be used such as thediglycidyl ether of Bisphenol F, or the diglycidyl ether of resorcinol.For improved thermal oxidative and UV stability, cycloaliphatic epoxiescan be used.

[0162] In another aspect of the invention, one or more primary and/orsecondary amines can be reacted with excess anhydride, such as maleicanhydride

[0163] to form a polymer having one or more terminal carboxylfunctionalities —COOH.

[0164] In yet another aspect of the invention, one or more primaryor/and secondary amines can be reacted with glycidyl methacrylate

[0165] to form a polymer having one or more terminal olefinic groups—C(R)═CH₂, wherein R can be methyl).

[0166] In yet another aspect of the invention, one or more primaryor/and secondary amines can be reacted with glycidol

[0167] to provide a hydroxyl terminated polymer with an epoxy group.

[0168] Condensation polymers can also be prepared. For example, apolyamide condensation polymer can be synthesized from a telechelicdiamine and a dicarboxylic acid.

[0169] The skilled artisan will appreciate that these and otherreactions can be conducted on one or more terminal ends of the polymersof the invention.

[0170] In addition, when the living chain end is reacted with aprotected functionalized electrophile, the resultant protectedfunctionality can also be deprotected, and the liberated functionalitycan optionally be reacted with one or more comonomers to polymerize afunctional end thereof. Exemplary comonomers include without limitationcyclic ethers, diamines, diisocyanates, polyisocyanates, di-, poly- andcyclic amides, di- and polycarboxylic acids, diols, polyols, anhydrides,and the like and mixtures thereof. For example, functionalized polymerscan be further reacted with monofunctional monomers, such ascaprolactam, or other lactams, to form a polyamide block polymersegment, or cyclic ethers such ethylene oxide to form polyether blocks;or with difunctional monomers, such as diacids or anhydrides anddiamines to form polyamide blocks, or diacids or anhydrides or lactonesand diols to form polyester blocks, or diols and polyols withdiisocyanates or polyisocyanates to form polyurethane blocks.Polyisocyanates or polyfunctional polyols are examples of polyfunctionalmonomers. The functional group may also be reacted with a suitable agentcontaining a reactive olefinic bond, such as a styrenic or acrylicfunctionality, such as methacroyl chloride, which will act to change thenature of the functionality and provide a “macromonomer” capable ofpolymerizing with other free radically polymerizable monomers.

[0171] In yet another aspect of the invention, two or more livingpolymers can be linked using a coupling or linking agent as known in theart. In one embodiment of this aspect of the invention, the linkingagent is a difunctional linking agent. The resultant homotelechelicpolymer is represented by the below formula:

L-[Pm-Qn-Z-N(R¹)(R²)]₂

[0172] wherein:

[0173] each R¹, R², P, Q, Z, m and n independently have the meaningsascribed above; and

[0174] L is a residue of a difunctional linking agent, such as SiMe₂residue derived form the difunctional linking agent SiMe₂Cl₂.

[0175] In another embodiment of this aspect of the invention, thelinking agent is a multifunctional linking agent. The resultant star ormulti-branched polymer is represented by the below formula:

L′-[Pm-Qn-Z-N(R¹)(R²)]_(v)

[0176] wherein:

[0177] each R¹, R², P, Q, Z, m and n independently have the meaningsascribed above;

[0178] L′ is a residue of a multifunctional linking agent, such asdivinylbenzene; and

[0179] v is from 3 to 30. As the skilled artisan will appreciate, eachR¹, R², P, Q, Z, m and n can differ if the coupled living polymers areprepared using different protected functionalized and/or non-functionalinitiators. Such polymers prepared using different protectedfunctionalized initiators and/or non-functional initiators can bepresented as follows:

L′-[Pm-Qn-Z-N(R¹)(R²)]_(30-v)[Pm—B]_(v)

[0180] wherein:

[0181] R¹, R², P, Q, Z, m, n, L′, and v have the meanings ascribedabove; and

[0182] each [Pm—B] can be the same or different and each P and m is asdefined above and each B is independently selected from the residue ofan alkyllithium initiator (i.e., a non-functional initiator) or aprotected functionalized initiator, in which the protecting group isintact or removed. The skilled artisan will appreciate that each arm canbe the same length or different lengths and can include the same ordifferent monomer composition.

[0183] As discussed above, these homotelechelic and star ormulti-branched polymers can be hydrogenated, deprotected and/or furtherreacted with one or more comonomers to form polymer segments.Particularly preferred polymers include homotelechelic and star ormultibranched polymers having primary and/or secondary amine groups, aswell as their hydrogenated analogs. As noted above, primary aminesresult from the removal of both protecting groups R¹ and R² andsecondary amines result from the removal of protecting group R¹. Theprimary and secondary amine groups are represented generally by theformula —N(H)R, in which R is hydrogen (primary amine) or R² as definedabove.

[0184] The molecular architecture of compounds of the present inventioncan be precisely controlled. The degree of functionality can be adjustedby simply varying the ratio of tertiary amino functional initiator tocoupling agent. Further, the monomer identity, the monomer compositionand molecular weight can be independently manipulated by varying themonomer charged. Finally, the number of polymer arms can be adjusted byvarying the nature of the coupling agent, and the ratio of livingpolymer to the coupling agent.

[0185] Non-hydrogenated linear or radial polymers prepared with theamine initiators of the present invention, including homopolymers ofdienes, block or random copolymers of different dienes, or block orrandom copolymers of dienes and alkenylsubstituted aromatic monomers,possessing tertiary amine functional groups, are useful for productionof elastomeric compounds exhibiting reduced hysteresis characteristics.Introduction of functional groups, particularly amino functional groupsto the termini of polymer chains of polymers used in tire compounds inparticular, has resulted in lowered hysteresis properties which areassociated with reduced rolling resistance and heat build-up duringoperation of the tire. Examples of the use of amine functional polymersfor such applications are described in U.S. Pat. Nos. 5,959,048,5,935,893, 5,932,662, 5,916,961, 5,912,343, 5,902,856, 5,880,206,5,502,131, 5,496,940, 5,491,230, 5,332,810, 5,274,106, 5,238,893,5,219,942, 5,216,080, 5,115,006, 4,614,771, the disclosures of which areincorporated herein by reference.

[0186] The present invention will be further illustrated by thefollowing non-limiting examples.

Preparation of Initiators EXAMPLE 1 Preparation of Initiator Precursor3-[(N-benzyl-N-methyl)amino]-1-propylchloride

[0187] To a stirred suspension of K₂CO₃ (200 g, 1.5 mole) in cyclohexane200 mL and 1-bromo-3-chloropropane (“BCP”) (540 g, 3.4 mole) was addeddropwise over a period of 1 hour at 20° C. benzylmethyl amine (272 g,2.24 mole). After complete addition the reaction was allowed to stir foran additional 20 hours. The crude reaction mixture was filtered and thenwashed with saturated NaCl (3×100 mL). The organic phase was extractedwith 3N HCl (3×100 mL). The resulting aqueous phase, containing thedesired product as the hydrochloric salt, was washed with hexanes (3×100mL) to remove any residual BCP. The aqueous phase was subsequentlybasified with 50 wt % NaOH and extracted with cyclohexane (3×100 mL).After solvent removal 220 g (50% yield) of the title compound wasisolated as a yellow oil.

EXAMPLE 2

[0188] Preparation of 3-[(N-benzyl-N-methyl)amino]-1-propyllithium

[0189] To a 500 ml Morton/cleave flask reactor under argon atmospherewas added lithium powder (13.32 g, 1.92 mole) and 141 grams ofcyclohexane. To a constant addition funnel was added3-[(N-benzyl-N-methyl)amino]-1-propylchloride (70.93 g, 0.34 mol) and83.3 grams cyclohexane. Immediately before beginning the addition, thelithium metal mixture was heated to 53° C. using a heating mantel.Dropwise addition of the feed solution was performed while maintainingthe reaction temperature at 50° C. A cooling bath of hexane, to whichdry ice was added periodically, was employed to maintain a reactiontemperature between 48° to 51° C. The total addition time was 1.22 hourswith an average stirring rpm of 925. The reaction mixture was stirred atleast one hour after the feed was completed. This mixture was thenpumped through a ⅜″ teflon tube to a pressure filter that containedabout 10 grams of filter aid and filtered under an argon atmosphere. Thereactor was then rinsed 3×50 ml cyclohexane, each time transferred tothe muds that were also washed with the rinse. The final product was 420g of light amber solution. Analysis by WE titration indicated a 99%yield of active base (0.809 mole/kg). GC-MS (TMS derivative): Calculatedfragment masses: 235, 220, 134, 91, 73; Observed fragment masses: 235,220, 134, 91, 73.

EXAMPLE 3 Preparation of Initiator Precursor3-[(N,N-dibenzylamino]-1-propylchloride

[0190] To a stirred suspension of K₂CO₃ (200 g, 1.5 mole) in cyclohexane200 mL and 1-bromo-3-chloropropane (540 gms, 3.4 mole) is added dropwiseover a period of 1 h at 20° C. dibenzyl amine (442 g, 2.24 mole). Aftercomplete addition the reaction is allowed to stir for an additional 20h. The crude reaction mixture is filtered and then washed with saturatedNaCl (3×100 mL). The organic phase is extracted with 3N HCl (3×100 mL).The resulting aqueous phase, containing the desired product as thehydrochloric salt, is washed with hexanes (3×100 mL) to remove anyresidual BCP. The aqueous phase is subsequently basified with 50 wt %NaOH and extracted with cyclohexane (3×100 mL). After solvent removal324 g (53% yield) of the title compound was isolated as a yellow oil.

EXAMPLE 4 Preparation of 3-[(N,N-dibenzylamino]-1-propyllithium

[0191] To a 500 ml Morton/cleave flask reactor under argon atmosphere isadded lithium powder (13.32 g, 1.92 mole) and 141 grams of cyclohexane.To a constant addition funnel is added3-[(N,N-dibenzylamino]-1-propylchloride (92.8 g, 0.34 mol) and 83.3grams cyclohexane. Immediately before beginning the addition, thelithium metal mixture is heated to 53° C. using a heating mantel.Dropwise addition of the feed solution is performed while maintainingthe reaction temperature at 50° C. A cooling bath of hexane, to whichdry ice is added periodically, is employed to maintain a reactiontemperature between 48° to 51° C. The total addition time is 1.22 hourswith an average stirring rpm of 925. The reaction mixture is stirred atleast one hour after the feed was completed. This mixture is then pumpedthrough a ⅜″ teflon tube to a pressure filter that contains about 10grams of filter aid and is filtered under an argon atmosphere. Thereactor is then rinsed 3×50 ml cyclohexane, each time transferred to themuds that were also washed with the rinse. The final product is 420 g oflight amber solution. Analysis by WE titration indicates a 99% yield ofactive base (0.809 mole/kg).

EXAMPLE 5 Preparation of Initiator Precursor3-[(N-t-Butyl-N-methyl)amino]-1-propylchloride

[0192] To a stirred suspension of K₂CO₃ (200 g, 1.5 mole) in cyclohexane200 mL and l-bromo-3-chloropropane (540 gms, 3.4 mole) is added dropwiseover a period of 1 h at 20° C. t-butylmethyl amine (194 g, 2.24 mole).After complete addition the reaction is allowed to stir for anadditional 20 h. The crude reaction mixture is filtered and then washedwith saturated NaCl (3×100 mL). The organic phase is extracted with 3NHCl (3×100 mL). The resulting aqueous phase, containing the desiredproduct as the hydrochloric salt, is washed with hexanes (3×100 mL) toremove any residual BCP. The aqueous phase is subsequently basified with50 wt % NaOH and extracted with cyclohexane (3×100 mL). After solventremoval 186 g (51% yield) of the title compound is isolated as a yellowoil.

EXAMPLE 6 Preparation of 3-[(N-t-Butyl-N-methyl)amino]-1-propyllithium

[0193] To a 500 ml Morton/cleave flask reactor under argon atmosphere isadded lithium powder (13.32 g, 1.92 mole) and 141 grams of cyclohexane.To a constant addition funnel was added3-[(N-t-Butyl-N-methyl)amino]-1-propylchoride (55.6 g, 0.34 mol) and83.3 grams cyclohexane. Immediately before beginning the addition, thelithium metal mixture is heated to 53° C. using a heating mantel.Dropwise addition of the feed solution is performed while maintainingthe reaction temperature at 50° C. A cooling bath of hexane, to whichdry ice is added periodically, is employed to maintain a reactiontemperature between 48° to 51° C. The total addition time is 1.22 hourswith an average stirring rpm of 925. The reaction mixture is stirred atleast one hour after the feed is completed. This mixture is then pumpedthrough a ⅜″ teflon tube to a pressure filter that contains about 10grams of filter aid and filtered under an argon atmosphere. The reactoris then rinsed 3×50 ml cyclohexane, each time transferred to the mudsthat are also washed with the rinse. The final product is 420 g of lightamber solution. Analysis by WE titration indicated a 99% yield of activebase (0.809 mole/kg).

EXAMPLE 7 Preparation of Initiator Precursor3-[(N,N-di-t-Butyl)amino]-1-propylchloride

[0194] To a stirred suspension of K₂CO₃ (200 g, 1.5 mole) in cyclohexane200 mL and 1-bromo-3-chloropropane (540 gms, 3.4 mole) is added dropwiseover a period of 1 h at 20° C. di-t-butyl amine (289 g, 2.24 mole).After complete addition the reaction is allowed to stir for anadditional 20 h. The crude reaction mixture is filtered and then washedwith saturated NaCl (3×100 mL). The organic phase is extracted with 3NHCl (3×100 mL). The resulting aqueous phase, containing the desiredproduct as the hydrochloric salt, is washed with hexanes (3×100 mL) toremove any residual BCP. The aqueous phase is subsequently basified with50 wt % NaOH and extracted with cyclohexane (3×100 mL). After solventremoval 234 g (51% yield) of the title compound is isolated as a yellowoil.

EXAMPLE 8 Preparation of 3-[(N,N-di-t-Butyl)amino]-1-propyllithium

[0195] To a 500 ml Morton/cleave flask reactor under argon atmosphere isadded lithium powder (13.32 g, 1.92 mole) and 141 grams of cyclohexane.To a constant addition funnel is added3-[(N,N-di-t-butyl)amino]-1-propylchoride (69.7 g, 0.34 mol) and 83.3grams cyclohexane. Immediately before beginning the addition, thelithium metal mixture is heated to 53° C. using a heating mantel.Dropwise addition of the feed solution is performed while maintainingthe reaction temperature at 50° C. A cooling bath of hexane, to whichdry ice is added periodically, is employed to maintain a reactiontemperature between 48° to 51° C. The total addition time is 1.22 hourswith an average stirring rpm of 925. The reaction mixture is stirred atleast one hour after the feed is completed. This mixture is then pumpedthrough a ⅜″ teflon tube to a pressure filter that contains about 10grams of filter aid and filtered under an argon atmosphere. The reactoris then rinsed 3×50 ml cyclohexane, each time transferred to the mudsthat were also washed with the rinse. The final product is 428.90 g oflight amber solution. Analysis by WE titration indicated a 99% yield ofactive base (0.809 mole/kg).

Preparation of Polymers EXAMPLE 9 Preparation of Protected-Alpha-3°Amine Functionalized Polyisoprene

[0196] A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N-benzyl-N-methyl)amino]-1-propyllithium 0.82 mmoles (0.14 gramsactive of 14.0 wt % in cyclohexane), and purified cyclohexane (195 g).The reactor is then flame sealed off. Diethylether 23 grams (0.31 mole)was added from a break-seal ampoule. Purified isoprene monomer (10.20grams, 150 mmoles) is added from a break-seal ampoule. The reactionmixture is stirred for twenty four hours at room temperature. Theliving, functionalized poly(isoprenyl)lithium is terminated withdegassed methanol from the last ampoule.2,6-Di-tert-butyl-4-methylphenol (BHT, 0.01%) is added to the polymersolution as an antioxidant. The resultant protected, functionalizedpolymer is isolated by concentration of the organic solution. Theresultant functionalized polyisoprene polymer is characterized by SEC(polyisoprene standards), and had the following properties: M_(n)=5,200g/mole, M_(w)=5,300 g/mole, M_(w)/M_(n)=1.03. ¹H NMR verifies amicrostructure of 55% 1,4 enchainment, and the presence of the benzylprotecting group on the amine functionality.

EXAMPLE 10

[0197] Preparation of Alpha-2° Amine Functionalized Polyisoprene

[0198] A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N-benzyl-N-methyl)amino]-1-propyllithium 0.82 mmoles (0.14 gramsactive of 14.0 wt % in cyclohexane), and purified cyclohexane (195 g).The reactor is then flame sealed off. Diethylether 23 grams (0.31 mole)was added from a break-seal ampoule. Purified isoprene monomer (10.20grams, 150 mmoles) is added from a break-seal ampoule. The reactionmixture is stirred for twenty four hours at room temperature. Theresulting reaction mixture is transferred to a 500 mL autoclave andsparged with hydrogen at 45° C. The reactor is pressurized to 700 psigwith hydrogen and a Ni/Al catalyst is added slowly to control theresulting exothermic reaction. Enough catalyst is added to achieve asolution concentration of nickel to 100 ppm. (The catalyst is preparedin advance by reacting 1 molar eq. of nickel(II) 2-ethylhexanote with 2molar eq. of triethylaluminum in cyclohexane). After 2 hr ofhydrogenation, the reaction is allowed to cool to room temperature,depressurized and purged with nitrogen. The resultant functionalizedpolymer is precipitated into a large amount of methanol, filtered andwashed with additional methanol. The resultant hydrogenatedfunctionalized polyisoprene polymer is characterized by ¹H NMR whichverifies near quantitative hydrogenation (>97%) of the unsaturation inthe backbone and deprotection (>97%) of the benzyl protecting group fromthe amine functionality to afford an alpha secondary amine.

EXAMPLE 11 Preparation of Alpha, Omega-2° Amine FunctionalizedPolyisoprene

[0199] A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N-benzyl-N-methyl)amino]-1-propyllithium 0.82 mmoles (0.14 gramsactive of 14.0 wt % in cyclohexane), and purified cyclohexane (195 g).The reactor is then flame sealed off. Diethylether 23 grams (0.31 mole)is added from a break-seal ampoule. Purified isoprene monomer (10.20grams, 150 mmoles) is added from a break-seal ampoule. The reactionmixture is stirred for twenty four hours at room temperature. To theliving polymer is added 3-[(N-benzyl-N-methyl)amino]-1-propylchoride(0.16 g, 0.9 mmoles) and is stirred for an additional 15 h at roomtemperature. The resulting reaction mixture is transferred to a 500 mLautoclave and sparged with hydrogen at 45° C. The reactor is pressurizedto 700 psig with hydrogen and a Ni/Al catalyst is added slowly tocontrol the resulting exothermic reaction. Enough catalyst is added toachieve a solution concentration of nickel to 100 ppm. (The catalyst isprepared in advance by reacting 1 molar eq. of nickel(II)2-ethylhexanote with 2 molar eq. of triethylaluminum in cyclohexane).After 2 hr of hydrogenation, the reaction is allowed to cool to roomtemperature, depressurized and purged with nitrogen. The resultanthydrogenated functionalized polyisoprene polymer is characterized by ¹HNMR which verifies near quantitative hydrogenation (>97%) of theunsaturation in the backbone and deprotection (>97%) of the benzylprotecting groups from the amine functionality to afford saturatedpolyisoprene with alpha, omega secondary amine functionalities.

EXAMPLE 12

[0200] Preparation of Protected-Alpha-3° AmineFunctionalized-Polybutadiene

[0201] A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N-benzyl-N-methyl)amino]-1-propyllithium 0.82 mmoles (0.14 gramsactive of 14.0 wt % in cyclohexane), and purified cyclohexane (I 95 g).The reactor is then flame sealed off. Diethylether 23 grams (0.31 mole)was added from a break-seal ampoule. Purified butadiene monomer (8.10grams, 150 mmoles) is added from a break-seal ampoule. The reactionmixture is stirred for twenty four hours at room temperature. Theliving, functionalized poly(butadienyl)lithium is terminated withdegassed methanol from the last ampoule.2,6-Di-tert-butyl-4-methylphenol (BHT, 0.01%) is added to the polymersolution as an antioxidant. The resultant protected, functionalizedpolymer is isolated by concentration of the organic solution. Theresultant functionalized polybutadiene polymer is characterized by SEC(polybutadiene standards), and had the following properties: M_(n)=5,200g/mole, M_(w)=5,300 g/mole, M_(w)/M_(n)=1.03. ¹H NMR indicates themicrostructure is 55% 1,4 enchainment, and the presence of the benzylprotecting group on the amine functionality.

EXAMPLE 13 Preparation of Alpha-2° Amine Functionalized Polybutadiene

[0202] A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N-benzyl-N-methyl)amino]-1-propyllithium 0.82 mmoles (0.14 gramsactive of 14.0 wt % in cyclohexane), and purified cyclohexane (195 g).The reactor is then flame sealed off. Diethylether 23 grams (0.31 mole)was added from a break-seal ampoule. Purified butadiene monomer (8.10grams, 150 mmoles) is added from a break-seal ampoule. The reactionmixture is stirred for twenty four hours at room temperature. Theresulting reaction mixture is transferred to a 500 mL autoclave andsparged with hydrogen at 45° C. The reactor is pressurized to 700 psigwith hydrogen and a Ni/Al catalyst is added slowly to control theresulting exothermic reaction. Enough catalyst is added to achieve asolution concentration of nickel to 100 ppm. The catalyst is prepared inadvance by reacting 1 molar eq. of nickel(II) 2-ethylhexanote with 2molar eq. of triethylaluminum in cyclohexane). After 2 hr ofhydrogenation, the reaction is allowed to cool to room temperature,depressurized and purged with nitrogen. The resultant functionalizedpolymer is precipitated into a large amount of methanol, filtered andwashed with additional methanol. The resultant hydrogenatedfunctionalized polybutadiene polymer is characterized by ¹H NMRindicating near quantitative hydrogenation (>97%) of the unsaturation inthe backbone and deprotection (>97%) of the benzyl protecting group fromthe amine functionality to afford a terminal secondary amine.

EXAMPLE 14 Preparation of Alpha, Omega-2° Amine FunctionalizedPolybutadiene

[0203] A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N-benzyl-N-methyl)amino]-1-propyllithium 0.82 mmoles (0.14 gramsactive of 14.0 wt % in cyclohexane), and purified cyclohexane (195 g).The reactor is then flame sealed off. Diethylether 23 grams (0.31 mole)is added from a break-seal ampoule. Purified butadiene monomer (8.10grams, 150 mmoles) is added from a break-seal ampoule. The reactionmixture is stirred for twenty four hours at room temperature. To theliving polymer is added 3-[(N-benzyl-N-methyl)amino]-1-propylchloride(0.16 g, 0.9 mmoles) and is stirred for an additional 15 h at roomtemperature. The resulting reaction mixture is transferred to a 500 mLautoclave and sparged with hydrogen at 45° C. The reactor is pressurizedto 700 psig with hydrogen-and a Ni/Al catalyst is added slowly tocontrol the resulting exothermic reaction. Enough catalyst is added toachieve a solution concentration of nickel to 100 ppm. (The catalyst isprepared in advance by reacting 1 molar eq. of nickel(II)2-ethylhexanote with 2 molar eq. of triethylaluminum in cyclohexane).After 2 hr of hydrogenation, the reaction is allowed to cool to roomtemperature, depressurized and purged with nitrogen. The resultanthydrogenated functionalized polybutadiene polymer is characterized by ¹HNMR which verifies near quantitative hydrogenation (>97%) of theunsaturation in the backbone and deprotection (>97%) of the benzylprotecting groups from the amine functionality to afford saturatedpolybutadiene with alpha, omega secondary amine functionalities.

EXAMPLE 15 Preparation of Protected-Alpha-3° Amine FunctionalizedPolyisoprene

[0204] A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N,N-dibenzylamino]-1-propyllithium 0.82 mmoles (0.16 grams active of14.0 wt % in cyclohexane), and purified cyclohexane (195 g). The reactoris then flame sealed off. Diethylether 23 grams (0.31 mole) is addedfrom a break-seal ampoule. Purified isoprene monomer (10.20 grams, 150mmoles) is added from a break-seal ampoule. The reaction mixture isstirred for twenty four hours at room temperature. The living,functionalized poly(isoprenyl)lithium is terminated with degassedmethanol from the last ampoule. 2,6-Di-tert-butyl-4-methylphenol (BHT,0.01%) is added to the polymer solution as an antioxidant. The resultantprotected, functionalized polymer is isolated by concentration of theorganic solution. The resultant functionalized polyisoprene polymer ischaracterized by SEC (polyisoprene standards), and had the followingproperties: M_(n)=5,200 g/mole, M_(w)=5,300 g/mole, M_(w)/M_(n)=1.03. ¹HNMR verifies a microstructure of 55% 1,4 enchainment, and the presenceof the benzyl protecting group on the amine functionality.

EXAMPLE 16 Preparation of Alpha-1° Amine Functionalized Polyisoprene

[0205] A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N,N-dibenzylamino]-1-propyllithium 0.82 mmoles (0.16 grams active of14.0 wt % in cyclohexane), and purified cyclohexane (195 g). The reactoris then flame sealed off. Diethylether 23 grams (0.31 mole) was addedfrom a break-seal ampoule. Purified isoprene monomer (10.20 grams, 150mmoles) is added from a break-seal ampoule. The reaction mixture isstirred for twenty four hours at room temperature. The resultingreaction mixture is transferred to a 500 mL autoclave and sparged withhydrogen at 45° C. The reactor is pressurized to 700 psig with hydrogenand a Ni/Al catalyst is added slowly to control the resulting exothermicreaction. Enough catalyst is added to achieve a solution concentrationof nickel to 100 ppm. (The catalyst is prepared in advance by reacting 1molar eq. of nickel(II) 2-ethylhexanote with 2 molar eq. oftriethylaluminum in cyclohexane). After 2 hr of hydrogenation, thereaction is allowed to cool to room temperature, depressurized andpurged with nitrogen. The resultant functionalized polymer isprecipitated into a large amount of methanol, filtered and washed withadditional methanol. The resultant hydrogenated functionalizedpolyisoprene polymer is characterized by ¹H NMR which verifies nearquantitative hydrogenation (>97%) of the unsaturation in the backboneand deprotection (>97%) of the benzyl protecting group from the aminefunctionality to afford a terminal primary amine.

EXAMPLE 17 Preparation of Alpha, Omega-1° Amine FunctionalizedPolyisoprene

[0206] A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N,N-dibenzylamino]-1-propyllithium 0.82 mmoles (0.16 grams active of14.0 wt % in cyclohexane), and purified cyclohexane (195 g). The reactoris then flame sealed off. Diethylether 23 grams (0.31 mole) was addedfrom a break-seal ampoule. Purified isoprene monomer (10.20 grams, 150mmoles) is added from a break-seal ampoule. The reaction mixture isstirred for twenty four hours at room temperature. To the living polymeris added 3-[(N,N-dibenzylamino]-1-propylchloride (0.25 g, 0.9 mmoles)and is stirred for an additional 15 h at room temperature. The resultingreaction mixture is transferred to a 500 mL autoclave and sparged withhydrogen at 45° C. The reactor is pressurized to 700 psig with hydrogenand a Ni/Al catalyst is added slowly to control the resulting exothermicreaction. Enough catalyst is added to achieve a solution concentrationof nickel to 100 ppm. (The catalyst is prepared in advance by reacting 1molar eq. of nickel(II) 2-ethylhexanote with 2 molar eq. oftriethylaluminum in cyclohexane). After 2 hr of hydrogenation, thereaction is allowed to cool to room temperature, depressurized andpurged with nitrogen. The resultant hydrogenated functionalizedpolyisoprene polymer is characterized by ¹H NMR which verifies nearquantitative hydrogenation (>97%) of the unsaturation in the backboneand deprotection (>97%) of the benzyl protecting groups from the aminefunctionality to afford saturated polyisoprene with alpha, omega primaryamine functionalities.

EXAMPLE 18 Preparation of Protected-Alpha-3° AmineFunctionalized-Polybutadiene

[0207] A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N,N-dibenzylamino]-1-propyllithium 0.82 mmoles (0.16 grams active of14.0 wt % in cyclohexane), and purified cyclohexane (195 g). The reactoris then flame sealed off. Diethylether 23 grams (0.31 mole) was addedfrom a break-seal ampoule. Purified butadiene monomer (8.10 grams, 150mmoles) is added from a break-seal ampoule. The reaction mixture isstirred for twenty four hours at room temperature. The living,functionalized poly(butadienyl)lithium is terminated with degassedmethanol from the last ampoule. 2,6-Di-tert-butyl-4-methylphenol (BHT,0.01%) is added to the polymer solution as an antioxidant. The resultantprotected, functionalized polymer is isolated by concentration of theorganic solution. The resultant functionalized polybutadiene polymer ischaracterized by SEC (polybutadiene standards), and had the followingproperties: M_(n)=5,200 g/mole, M_(w)=5,300 g/mole, M_(w)/M_(n)=1.03. ¹HNMR indicates the microstructure is 55% 1,4 enchainment, and thepresence of the benzyl protecting groups on the amine functionality.

EXAMPLE 19 Preparation of Alpha-1° Amine Functionalized Polybutadiene

[0208] A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N,N-dibenzylamino]-1-propyllithium 0.82 mmoles (0.16 grams active of14.0 wt % in cyclohexane), and purified cyclohexane (195 g). The reactoris then flame sealed off. Diethylether 23 grams (0.31 mole) was addedfrom a break-seal ampoule. Purified butadiene monomer (8.10 grams, 150mmoles) is added from a break-seal ampoule. The reaction mixture isstirred for twenty four hours at room temperature. The resultingreaction mixture is transferred to a 500 mL autoclave and sparged withhydrogen at 45° C. The reactor is pressurized to 700 psig with hydrogenand a Ni/Al catalyst is added slowly to control the resulting exothermicreaction. Enough catalyst is added to achieve a solution concentrationof nickel to 100 ppm. (The catalyst is prepared in advance by reacting 1molar eq. of nickel (II) 2-ethylhexanote with 2 molar eq. oftriethylaluminum in cyclohexane). After 2 hr of hydrogenation, thereaction is allowed to cool to room temperature, depressurized andpurged with nitrogen. The resultant functionalized polymer isprecipitated into a large amount of methanol, flittered and washed withadditional methanol. The resultant hydrogenated functionalizedpolybutadiene polymer is characterized by ¹H NMR verifying nearquantitative hydrogenation (>97%) of the unsaturation in the backboneand deprotection (>97%) of the benzyl protecting groups from the aminefunctionality to afford an alpha primary amines.

EXAMPLE 20 Preparation of Alpha, Omega-2° Amine FunctionalizedPolybutadiene

[0209] A 500 ml. glass reactor is equipped with three break-seal reagentampoules, a sampling port attached with a Teflon® stopcock, an inlettube fitted with a septum cap, and a magnetic stir bar. This reactor isflame sealed to a high vacuum line, and evacuated at 120° C. for 8hours. The flask is refilled with dry argon, and allowed to cool to roomtemperature. The reactor is charged with3-[(N,N-dibenzylamino]-1-propyllithium 0.82 mmoles (0.16 grams active of14.0 wt % in cyclohexane), and purified cyclohexane (195 g). The reactoris then flame sealed off. Diethylether 23 grams (0.31 mole) was addedfrom a break-seal ampoule. Purified butadiene monomer (8.10 grams, 150mmoles) is added from a break-seal ampoule. The reaction mixture isstirred for twenty four hours at room temperature. To the living polymeris added 3-[(N,N-dibenzylamino]-1-propylchloride (0.25 g, 0.9 mmoles)and is stirred for an additional 15 h at room temperature. The resultingreaction mixture is transferred to a 500 mL autoclave and sparged withhydrogen at 45° C. The reactor is pressurized to 700 psig with hydrogenand a Ni/Al catalyst is added slowly to control the resulting exothermicreaction. Enough catalyst is added to achieve a solution concentrationof nickel to 100 ppm. (The catalyst is prepared in advance by reacting 1molar eq. of nickel (II) 2-ethylhexanote with 2 molar eq. oftriethylaluminum in cyclohexane). After 2 hr of hydrogenation, thereaction is allowed to cool to room temperature, depressurized andpurged with nitrogen. The resultant hydrogenated functionalizedpolybutadiene polymer is characterized by ¹H NMR which indicates nearquantitative hydrogenation (>97%) of the unsaturation in the backboneand deprotection (>97%) of the benzyl protecting groups from the aminefunctionality to afford saturated polybutadiene with alpha, omegaprimary amine functionalities.

[0210] Many modifications and other embodiments of the invention willcome to mind to one skilled in the art to which this invention pertainshaving the benefit of the teachings presented in the foregoingdescriptions and the associated drawings. Therefore, it is to beunderstood that the invention is not to be limited to the specificembodiments disclosed and that modifications and other embodiments areintended to be included within the scope of the appended claims.Although specific terms are employed herein, they are used in a genericand descriptive sense only and not for purposes of limitation.

That which is claimed:
 1. A compound of the formula:

wherein: M is an alkali metal selected from the group consisting oflithium, sodium and potassium; Z is a branched or straight chainhydrocarbon connecting group which contains 3-25 carbon atoms,optionally substituted with aryl or substituted aryl; Q is a saturatedor unsaturated hydrocarbyl group derived by the incorporation of one ormore unsaturated organic compounds into the M-Z linkage; n is from 0 to5; R¹ is selected from the group consisting of aralkyl, allyl, tertiaryalkyl and methyl; and R² is the same as R¹, with the proviso that whenR¹ is methyl, R² is not C1-C4 alkyl, or R² is different from R¹ andselected from the group consisting of alkyl, substituted alkyl, alkoxy,substituted alkoxy, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, andsubstituted heterocycloalkyl, with the proviso that when R² is not thesame as R¹, then R² is more stable under conditions used to remove R¹,or R¹ and R² together with the nitrogen atom to which they are attachedform

 wherein y is from 1 to 4 and each R¹¹ is independently selected fromthe group consisting of hydrogen, alkyl, substituted alkyl, aryl,substituted aryl, cycloalkyl, substituted cycloalkyl, alkoxy,substituted alkoxy, heteroaryl, substituted heteroaryl,heterocycloalkyl, and substituted heterocycloalkyl.
 2. The compound ofclaim 1, wherein the protecting group R¹ is aralkyl, allyl, or tertiaryalkyl.
 3. The compound of claim 2, wherein R¹ is benzyl or benzylderivative.
 4. The compound of claim 2, wherein R¹ is allyl.
 5. Thecompound of claim 2, wherein R¹ is tertiary alkyl.
 6. The compound ofclaim 5, wherein R¹ is tertiary butyl.
 7. The compound of claim 2,wherein R² is the same as R¹.
 8. The compound of claim 2, wherein R² ismethyl.
 9. The compound of claim 2, wherein R¹ and R² together with thenitrogen atom to which they are attached form


10. The compound of claim 9, wherein each R¹¹ is hydrogen.
 11. Thecompound of claim 1, wherein said compound is3-[(N-benzyl-N-methyl)amino]-1-propyllithium.
 12. The compound of claim1, wherein said compound is 3-[(N,N-dibenzyl)amino]-1-propyllithium. 13.The compound of claim 1, wherein said compound is3-[(N-tert-butyl-N-methyl)amino]-1-propyl lithium.
 14. The compound ofclaim 1, wherein said compound is3-[(N,N-di-tert-butyl)amino]-1-propyllithium.
 15. The compound of claim1, wherein M is lithium.
 16. The compound of claim 1, wherein n is zero.17. The compound of claim 1, wherein n is greater than zero.
 18. Thecompound of claim 17, wherein Q is derived by incorporation of one ormore compounds selected from the group consisting of conjugated dienehydrocarbons, alkenylsubstituted aromatic compounds, and mixturesthereof.
 19. The compound of claim 18, wherein said conjugated diene isselected from the group consisting of 1,3-butadiene, isoprene,2,3-dimethyl-1,3-butadiene, 1,3-pentadiene (piperylene), myrcene,2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-pentadiene,1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3-heptadiene,3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene,3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-pentadiene,4,5-diethyl-1,3-octadiene, 2,4-diethyl-1,3-butadiene,2,3-di-n-propyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene, andmixtures thereof.
 20. The compound of claim 18, wherein saidalkenylsubstituted aromatic compound is selected from the groupconsisting of styrene, alpha-methylstyrene, vinyltoluene,2-vinylpyridine, 4-vinylpyridine, 1-vinylnaphthalene,2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene,2-alpha-methylvinylnaphathalene, 1,2-diphenyl-4-methyl-1-hexene, alkyl,cycloalkyl, aryl, alkaryl and aralkyl derivatives thereof and mixturesthereof.
 21. A process for making amine functionalized compounds,comprising reacting one or more omega-tertiary-amino-1-haloalkanes ofthe formula

wherein: X is halide; Z is a branched or straight chain hydrocarbonconnecting group which contains 3-25 carbon atoms, optionallysubstituted with aryl or substituted aryl; R¹ is a protecting groupselected from the group consisting of aralkyl, allyl, tertiary alkyl andmethyl; and R² is the same as R¹, with the proviso that when R¹ ismethyl, R² is not C1-C4 alkyl, or R² is different from R¹ and selectedfrom the group consisting of alkyl, substituted alkyl, alkoxy,substituted alkoxy, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, andsubstituted heterocycloalkyl, with the proviso that when R² is not thesame as R¹, then R² is more stable under conditions used to remove R¹,or R¹ and R² together with the nitrogen atom to which they are attachedform

 wherein y is from 1 to 4 and each R¹¹ is independently selected fromthe group consisting of hydrogen, alkyl, substituted alkyl, aryl,substituted aryl, cycloalkyl, substituted cycloalkyl, alkoxy,substituted alkoxy, heteroaryl, substituted heteroaryl,heterocycloalkyl, and substituted heterocycloalkyl,  with an alkalimetal in an alkane, cycloalkane, or aromatic reaction solvent ormixtures of such solvents to form one or more compounds of the formula

 wherein M is an alkali metal and Z, R¹, and R² are the same definedabove; and optionally reacting said amine compound with one or moreunsaturated organic compounds to form a compound having a saturated orunsaturated hydrocarbyl group Q between Z and M of the formula

 wherein: Q is a saturated or unsaturated hydrocarbyl group derived bythe incorporation of one or more unsaturated organic compounds; n isfrom 0 to 5; and Z, R¹, and R² are the same defined above.
 22. Theprocess of claim 21, wherein the protecting group R¹ is aralkyl, allyl,or tertiary alkyl.
 23. The process of claim 22, wherein R¹ is benzyl orbenzyl derivative.
 24. The process of claim 22, wherein R¹ is allyl. 25.The process of claim 22, wherein R¹ is tertiary alkyl.
 26. The processof claim 25, wherein R¹ is tertiary butyl.
 27. The process of claim 22,wherein R² is the same as R¹.
 28. The process of claim 22, wherein R² ismethyl.
 29. The process of claim 21, wherein said compound is3-[(N-benzyl-N-methyl)amino]-1-propyllithium.
 30. The process of claim21, wherein said compound is 3-[(N,N-dibenzyl)amino]-1-propyllithium.31. The process of claim 21, wherein said compound is3-[(N-tert-butyl-N-methyl)amino]-1-propyllithium.
 32. The process ofclaim 21, wherein said compound is3-[(N,N-di-tert-butyl)amino]-1-propyllithium.
 33. The process of claim21, wherein M is lithium.